Actinides: Computational Chemistry
Actinides: Computational Chemistry
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DOI：
10.1002/9781119951438.eibc2540
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发表时间：
2018-09
期刊：
影响因子：
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通讯作者：
M. Dolg;X. Cao
中科院分区：
文献类型：
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作者：
M. Dolg;X. Cao
简要回顾了计算锕系元素和反锕系元素原子和分子的电子结构的相对论量子化学从头计算方法。强调了相对论和电子相关效应对于重元素量子化学研究的重要性。此外，还需要超越狄拉克单电子相对论，并包括例如相对论双电子相互作用的布赖特相互作用，甚至包括量子电动力学的低阶贡献，以具体示例进行说明。总结了从头算量子化学计算坐标系的三个轴（哈密顿轴、单粒子基组轴和多粒子基组轴）上可能的条目。介绍并比较了全电子和仅价态相对论哈密顿量的几种选择，并讨论了考虑相对论效应的主要策略，包括计算中的自旋轨道相互作用和电子相关效应。对密度泛函理论应用于锕系和反锕系体系时出现的问题进行了一些评论。最后，一些选定的例子显示了当前可用的已知最重元素及其化学性质的理论研究方法的适用范围。
Relativistic quantum chemical ab initio methods for calculations of the electronic structures of actinide and transactinide atoms and molecules are briefly reviewed. The importance of relativistic and electron correlation effects for heavy‐element quantum chemical investigations is emphasized. In addition, the need to go beyond the Dirac one‐electron relativity and to include, for example, the Breit interaction for the relativistic two‐electron interaction or even low‐order contributions from quantum electrodynamics is shown for specific examples. The possible entries on the three axes of the coordinate system of ab initio quantum chemical calculations—Hamiltonian axis, one‐, and many‐particle basis set axes—are summarized. Several choices for relativistic Hamiltonians at the all‐electron and valence‐only level are introduced and compared, and the principal strategies to account for relativistic effects, including spin–orbit interaction and electron correlation effects in calculations, are discussed. Some remarks on problems when applying density functional theory to actinide and transactinide systems are made. Finally, a few selected examples show the range of applicability of the currently available methods for theoretical investigations of the heaviest known elements and their chemistry.